KR20110015463A - Electronic device comprising metal complexes - Google Patents

Abstract

The present invention relates to organic electroluminescent devices comprising metal complexes according to formula (1) and metal complexes for use in organic electroluminescent devices.

Description

ELECTRONIC DEVICE COMPRISING METAL COMPLEXES

The structure of organic electroluminescent devices (OLEDs) in which organic semiconductors are employed as functional materials are described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. Emitting materials employed here are organometallic complexes which gradually exhibit phosphorescence instead of fluorescence (M. A. Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum mechanical reasons, up to a fourfold increase in energy and power efficiency is possible by using organometallic compounds as phosphorescent emitters. In general, however, there is still a need for improvements in OLEDs exhibiting triplet emission, especially with regard to the stability, efficiency, operating voltage and lifetime of the metal complex. Thus, further improvements are desirable here. In addition, for other compounds used in organic electroluminescent devices, such as matrix materials and charge transport materials, there is still a need for improvement.

According to the prior art, triplet emitters employed in phosphorescent OLEDs are usually iridium complexes. Improvements in these OLEDs have been achieved by employing metal complexes with polypodal ligands or cryptates, as a result of which the complexes have higher thermal stability, resulting in longer lifetimes of the OLEDs. (WO 04/081017, WO 05/113563, WO 06/008069). However, further improvements in the complex are still desirable in order to be able to employ the complexes in high quality and long life electroluminescent devices such as televisions or computer monitors.

Metal complexes are also employed in other functions in organic electroluminescent devices, for example Alq ₃ (aluminum tris (hydroxyquinolinate)) as an electron transport material, or BAlq (eg as a triplet matrix material or hole blocking material). For example, T. Tsuji et al., Journal of the Society of Information Display 2005, 13 (2), 117-122. Further improvement is still needed in the case of these materials for use in high quality electroluminescent devices.

It is therefore an object of the present invention to provide novel organic electroluminescent devices comprising metal complexes. Metal complexes can be employed here as emitters, matrix materials, hole blocking materials, electron transport materials, or depending on the metal used in particular, or can also be employed in other functions in the OLED. In particular, there is still a need for improvement in the case of red, green and blue phosphorescent metal complexes.

Surprisingly, certain organic electroluminescent devices comprising metal chelate complexes, described in more detail below, accomplish this goal and as a result, the organic electroluminescent device is significantly improved, especially with regard to lifetime, efficiency and heat safety. I found out. This applies in particular to green and blue phosphorescent electroluminescent devices. Accordingly, the present invention relates to organic electroluminescent devices comprising these complexes. The invention also relates to particularly suitable metal complexes that can be used in organic electroluminescent devices.

The prior art includes organic electroluminescent devices comprising metal complexes having tridentate or polydentate ligands (WO 04/108857), wherein the ligand represents a straight chain structure. However, from this disclosure it is not clear that it is possible to use the tridentate ligand in the form of a macrocycle, which may have advantages with regard to the use of the complex.

Specific metal complexes with tridentate ligands are also known from US 2008/0067925. Of these, three coordinating aryl or heteroaryl groups are linked to two divalent linking groups to form a tridentate straight chain ligand, which is coordinated to metals of Groups 8 to 10, in particular iridium or platinum. These ligands, together with monodentate ligands, bind to platinum, forming square planar complexes, where the coordination atoms of the ligands are coplanar with the metal atoms. However, from this disclosure it is not clear that it is also possible to use these tridentate ligands in the form of macrocycles, which may have advantages with regard to the use of the complex. Corresponding macrocyclic ligands result in different coordination geometries, in particular in metals, which means that coplanar coordination is no longer possible and coordination in octahedral complexes only occurs in face.

Metal complexes with tridentate, macrocyclic ligands are generally known (eg WO 07/079585, EP 1531193). However, these applications are only intended to use the metal complexes as catalytically active activators for oxygen removal in water-containing systems and for inorganic peroxide compounds in cleaning solutions for hard surfaces. List it. The suitability of metal complexes for organic electronic devices, in particular organic electroluminescent devices, is not apparent from these applications.

That is, this invention relates to the electronic device containing at least 1 metal complex of following formula (1).

At least one metal complex of formula (1) contains a metal M coordinated to a ligand of formula (2),

The following applies to the symbols and indices used herein.

L is, at each occurrence, identically or differently, a substituted or unsubstituted cyclic group, and in each case contains at least one donor atom or C atom or exocyclic donor atom in the ring, The cyclic group is bonded to the metal M; Groups L are connected to each other through groups Y;

Y, at each occurrence, identically or differently, is a substituted or unsubstituted atom from the third, fourth, fifth or sixth main group, in each case connecting two groups L;

L 1, in each presence, identically or differently, is a single-, two-, three-, four-, five-, or six-membered ligand that binds to metal M;

n is, equally or differently, at each occurrence, 0, 1, 2, 3, 4, 5 or 6, where n = 0 means that no group Y is present and a single bond is between two groups L To do;

p is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

The index p is here chosen such that the coordination number in metal M generally corresponds to the normal coordination number for this metal, depending on the metal. For main group and transition metals, the index p is usually of coordination number 4, 5 or 6, depending on the metal, i.e., if these coordination sites are not saturated by additional donor groups bonded to ligands L, index p Is usually 1, 2 or 3 for the main group and the transition metals. Especially for lanthanides, a coordination number of up to 12 is also known. It is generally known that metal coordination compounds have different coordination numbers, ie, to bind different numbers of ligands, depending on the metal and the oxidation state of the metal. Since the general expertise of the person skilled in the organometallic chemistry or coordination chemistry includes the desired coordination number of metal ions and metals in different oxidation states, the person skilled in the art uses a suitable number of additional ligands L1, whereby Depending on its oxidation state and on the exact structure of the ligand of formula (2), it will be easy to select the index p in a suitable manner.

The metal M in the compound of formula (1) is preferably a transition metal, an alkali metal, an alkaline earth metal, a main group metal or lanthanide from the third or fourth main group.

An electronic device is understood to mean an electronic device comprising an anode, a cathode and at least one layer, wherein this layer comprises at least one organic or organometallic compound or metal coordination compound. The organic electronic device according to the invention thus comprises at least one layer comprising an anode, a cathode and at least one compound of the formula (1) mentioned above. Preferred organic electronic devices are here organic electroluminescent devices (= organic light emitting diodes, OLEDs, PLEDs), organic integrated circuits, which comprise at least one compound of the above-mentioned formula (1) in at least one layer. (O-ICs), organic field-effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O-LETs), organic solar cells (O-SCs), organic light It is selected from the group consisting of detectors, organic light receptors, organic field-quench devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes (O-lasers). Organic electroluminescent devices are particularly preferred.

For the purposes of the present invention, donor atoms are considered to mean atoms having at least one free electron pair, which can be bonded to a metal atom or metal ion. The donor atom may be neutral here or negatively or positively charged. The donor atom is preferably neutral or negatively charged. Examples of neutral donor atoms are nitrogen in the heteroaromatic compound such as pyridine, or carbon in carbene form. Examples of anionic donor atoms are carbon that is part of an aromatic or heteroaromatic group, for example a carbon atom in a phenyl group, or nitrogen that is part of a five-membered heteroaromatic group, for example nitrogen in pyrrole that is bonded through nitrogen . For the purposes of the present invention, an extranuclear donor atom is considered to mean a donor atom, which is not part of the cyclic group L, but instead is bonded to L as a substituent and capable of bonding to a metal atom with at least one free electron pair. . Examples of extraneous donor atoms are oxygen in the form of phenolate, sulfur in the form of thiolate, nitrile, amine, imine, amide or imide in the form of nitrogen, phosphine or phosphite in the form of phosphorus or isonitrile or acetylide in the form of carbon .

The ligand of formula (2) is at least a tridentate, macrocyclic ligand which binds to the metal M via three groups L. For the purposes of the present invention, macrocycles are considered to mean rings having at least 10 ring atoms. As described in more detail below, for example, if substituents capable of bonding to metal M are also bonded to groups Y, the ligand of formula (2) may also have more than three coordination sites, for example It should be emphasized here that it can be four, five or six digits. Although the complex of formula (1) and the ligand of formula (2) are drawn in plan, these structures are not necessarily planar. Instead, the ligand of formula (2) typically adopts a cup-shaped form, similar to calixarene, where donor atoms are pointed towards the closed side of the cup, suitable for binding to the metal In form. Thereby, the additional coordination site to which the additional ligand can bind, described as L1 in the structure of formula (1), is stericly accessible to the metal. Thereby, for example, a tetrahedral complex, which is an octahedral complex in which the ligand of formula (2) is bound in a plane, is possible. In the same way, the substituents attached to the groups Y may also bind to the metal M in the compounds of the formula (1), depending on its structure. The form of the compounds of formula (1) is shown schematically below, where D generally represents the donor atom coordinated to the metal.

Hereinafter, embodiment of the compound of Formula (1) used preferably with an organic electronic device is described.

Preference is given to compounds of the formula (1) characterized by uncharged, ie electrically neutral. This is achieved in a simple manner by selecting the charge of any ligands L1 and groups L and the charge of the bridge units Y present in a manner that compensates for the charge of the complexed metal atom M.

More preferred are compounds of formula (1), characterized in that the sum of the valence electrons around the metal atom is 18. This preference is due to the special stability of these metal complexes (see, eg, Elschenbroich, Salzer, Organometallic Chemistry, Teubner Studienbucher, Stuttgart 1993).

The cyclic groups L may be homocyclic or heterocyclic and may be saturated, olefin, unsaturated or aromatic or heteroaromatic. In a preferred embodiment of the invention, the groups L may be the same or differently substituted or unsubstituted aryl or heteroaryl groups, or cyclic, saturated or unsaturated carbenes, in each presence. Preferred substituents are the radicals R shown below.

Preferred embodiments of the invention are organic electronic devices comprising at least one compound of formula (3).

Here, L1 and p have the same meaning as described above, and the following applies to the symbols and indices used.

M is a transition metal, lanthanide, alkali metal, alkaline earth metal or main group metal from the third or fourth main group;

D is the presence of, respectively, the same or different, C, N, P, CO ^-, CS ^-, C-NR ₂ or C-PR ₂ (the last mentioned here, four groups are O as hwanoe donor atoms, S , Is bound to the metal via N or P), or CN≡C, wherein this group is bound to the metal via carbon in the extraneous isonitrile group;

E is, at each occurrence, identically or differently, C or N;

Ar, at each occurrence, identically or differently, together with the groups E-D-E, forms an aryl or heteroaryl group having 5 to 40 aromatic ring atoms and is a group which may be substituted by one or more radicals R; Or when D represents a carbene carbon atom, Ar is a group together with the group E-D-E to form a cyclic saturating group having 5 to 10 aromatic ring atoms;

Y is the presence of, respectively, the same or ^{different, BR 1, B (R 1} ) 2 -, C (R 1) -, C (R 1) 2, Si (R 1) -, Si (R 1) ₂ , C (= O), C (= NR), N ⁻ , NR ¹ , N (R ¹ ) ₂ ⁺ , PR ¹ , P (R ¹ ) ₂ ⁺ , AsR ¹ , As (R ¹ ) ₂ ⁺ , P (= O) R ¹ , As (= O) R ¹ , P (= S) R ¹ , As (= S) R ¹ , O, S, S (R ¹ ) ⁺ , Se, Te, S (= O), S (= 0) ₂ , Se (= 0), Se (= 0) ₂ , Te (= 0) or Te (= 0) ₂ ;

R in each presence, identically or differently, H, deuterium, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , Si (R ² ) ₃ , B (OR ² ) ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , having from 1 to 40 C atoms Straight chain alkyl, alkoxy or thioalkoxy groups or straight chain alkenyl or alkynyl groups having 2 to 40 C atoms or branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy groups having 3 to 40 C atoms ( Each of which may be substituted by one or more radicals R ² , wherein one or more non-adjacent CH ₂ groups are R ² C═CR ² , C≡C, Si (R ² ) ₂ , Ge (R ² ) ₂ , By Sn (R ² ) ₂ , C = O, C = S, C = Se, C = NR ² , P (= O) (R ² ), SO, SO ₂ , NR ² , O, S or CONR ² It may be substituted, and wherein one or more H atoms by F, Cl, Br, I, can be replaced by CN, or NO _2), or one or more radicals R ² in each case Aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms which may be substituted by having 5 to 60 aromatic ring atoms which may hwandoel aromatic or heteroaromatic ring system, or one or more radicals R ^2, or A diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R ² , or a combination of these systems; Two or more of these substituents R may also form a monocyclic or polycyclic, aliphatic, aromatic and / or benzo-condensed ring system with one another;

R ^1, at each occurrence, identically or differently, is R or a group L2;

R ² in each presence, identically or differently, is an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having H, F or 1 to 20 C atoms, wherein also one or more H atoms are to be replaced by F Can be; Two or more substituents R ² here may also form a monocyclic or polycyclic, aliphatic or aromatic ring system with one another;

L 2 in each presence, identically or differently, is a donor group having from 1 to 40 C atoms, which can form additional bonds or coordination to the metal M and by one or more radicals R May be substituted;

n is 0, 1, 2, 3, 4, 5 or 6, provided that each index, equally or differently, at each occurrence does not represent 0 at the same time, where n = 0 is It means that Y is absent and a single bond is between two groups L.

At this point, it should be clearly emphasized that the radicals R ¹ bonded in the same group Y can also form a ring system with each other. That is, for example, if the group Y represents C (R ¹ ) ₂ , two radicals R ¹ bonded to the same carbon atom can also form a ring system with each other, thereby generating a spiro structure. Examples of ring systems possible here, in the case in which both groups R ¹ representing an alkoxy group to form a ring system with each other, a fluorine-phase (fluorene-like) group either, or both groups R ¹ is an alkoxy group to form a ring system together In the case of these, 1,3-dioxolane is used.

At this point, it should likewise be clearly emphasized that the radicals R ¹ bonded at the group Y can also form a ring system with the radicals R bonded at the group L2.

If the symbol D represents carbon, it is formally dependent on the embodiment and has a negative charge, ie a corresponding free ligand without metal M may contain a CH group at this point, or it may contain a neutral carbene carbon atom Indicates. If the symbol D represents nitrogen, this, depending on the embodiment, is a neutral donor atom or formally has a negative charge, ie the corresponding free ligand without the metal M contains N-H groups at this point. If symbol D represents phosphorus, this is a neutral donor atom.

For the purposes of the present invention, the donor group defined as L2 is taken to mean a chemical group or substituent having at least one donor atom capable of bonding to the metal M.

For the purposes of the present invention, aryl groups contain 6 to 40 C atoms, and for the purposes of the present invention, heteroaryl groups contain 2 to 40 C atoms, which is at least the sum of the C atoms and heteroatoms It is assumed that it is 5. Heteroatoms are preferably selected from N, O and / or S. An aryl group or heteroaryl group is here a simple aromatic ring, ie benzene, or a simple heteroaromatic ring, for example pyridine, pyrimidine, thiophene, or the like, or a condensed aryl or heteroaryl group such as naphthalene, anthracene, Phenanthrene, quinoline, isoquinoline and the like are understood to mean. For the purposes of the present invention, cyclic carbenes are cyclic groups which are bonded to the metal via neutral C atoms. The cyclic group can be saturated or unsaturated here. Preference is given here to Arduengo carbenes, ie carbenes in which two nitrogen atoms are bonded to a carbene C atom. 5-membered Arduengo carbene rings or other unsaturated 5-membered carbene rings are likewise regarded as aryl groups for the purposes of the present invention.

For the purposes of the present invention, an aromatic ring system contains 6 to 60 C atoms in the ring system. For the purposes of the present invention, heteroaromatic ring systems contain from 2 to 60 C atoms and at least one heteroatom in the ring system, assuming that the sum of the C atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O and / or S. For the purposes of the present invention, an aromatic or heteroaromatic ring system does not necessarily contain only aryl or heteroaryl groups, but instead a plurality of aryl or heteroaryl groups may also contain non-aromatic units (preferably of atoms other than H). Less than 10%), eg, a system, which may be interrupted by sp ³ -hybridized C, N or O atoms. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene and the like, also provide aromatic ring systems for the purposes of the present invention. And likewise two or more aryl groups are intended to mean systems which are interrupted by, for example, linear or cyclic alkyl groups or silyl groups.

For the purposes of the present invention, the C ₁ -to C ₄₀ -alkyl groups, wherein also the respective H atoms or CH ₂ groups can be substituted by the groups described above, are preferably radicals methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, tert-pentyl, 2-pentyl, cyclopentyl, n-hexyl, s -Hexyl, tert-hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n- Octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [2.2.2] octyl, 2-bicyclo [2.2.2] octyl, 2- (2,6-dimethyl) octyl, 3- (3,7- Dimethyl) octyl, trifluoromethyl, pentafluoroethyl or 2,2,2-trifluoroethyl. Alkenyl groups are considered to mean, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl or cyclooctenyl. Alkynyl groups are understood to mean, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octinyl. C ₁ -to C ₄₀ -alkoxy groups are preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-part It is considered to mean oxy or 2-methylbutoxy. Aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which in each case may be substituted by the aforementioned radicals R and which may be linked to an aromatic or heteroaromatic group via any desired position, are in particular benzene , Naphthalene, anthracene, phenanthrene, benzanthracene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobibi Fluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, trexen, isotrexene, spiroteluxene, spiroisotrexene, furan, benzofuran, isobenzofuran, Dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, ben -6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naftimidazole, phenanthrimidazole, pyridimidazole, Pyrazineimidazole, quinoxalineimidazole, oxazole, benzoxazole, naphthooxazole, antrooxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, Benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazanthracene, 2,7-diazaprene, 2,3-diazapyrene, 1,6-dia Zapyrene, 1,8-diazaprene, 4,5-diazaprene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine, phenothiazine, fluororubin, naphthyridine, Azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4- Oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5- Adiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5 Tetrazine, 1,2,3,4-tetrazin, 1,2,3,5-tetrazin, is believed to mean groups derived from purine, putridine, indolizine and benzothiadiazole.

Preference is given to compounds of the formulas (1) and (3), wherein M represents a transition metal, in particular a transition, coordinating, coordinating, coordinating, coordinating, chromium, molybdenum, tungsten, rhenium, ruthenium, Osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold, in particular molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, platinum and gold. Very particular preference is given to iridium and platinum. The metals can be here in various oxidation states. The metals described above are preferably Cr (O), Cr (II), Cr (III), Cr (IV), Cr (VI), Mo (O), Mo (II), Mo (III), Mo (IV) , Mo (VI) W (O), W (II), W (III), W (IV), W (VI), Re (I), Re (II), Re (III), Re (IV), Ru (II), Ru (III), Os (II), Os (III), Os (IV), Rh (I), Rh (III), Ir (I), Ir (III), Ir (IV), Ni (O), Ni (II), Ni (IV), Pd (II), Pt (II), Pt (IV), Cu (I), Cu (II), Cu (III), Ag (I), In Ag (II), Au (I), Au (III) and Au (V) oxidation states; Very particular preference is given to Mo (O), W (O), Re (I), Ru (II), Os (II), Rh (III), Ir (III) and Pt (II).

Also preferred are compounds of formula (1) or formula (3), wherein M represents a main group metal selected from the group consisting of lithium, sodium, magnesium, aluminum, gallium, indium or tin, or represents scandium, yttrium or lanthanum . Particularly preferred are Li (I), Na (I), Mg (II), Al (III), Ga (III), In (III), Sc (III), Y (III) or La (III), Al Very particular preference is given to (III).

In a preferred embodiment of the invention, index n represents 0, 1, 2 or 3, equally or differently in each presence, provided that all indexes do not represent 0 at the same time, particularly preferably all indexes are simultaneously 0, 1 or 2 is shown on the assumption that 0 is not shown. In a very particularly preferred embodiment of the invention, the index n represents 1 or 2, particularly 1, identically or differently in each presence.

In a preferred embodiment of the invention, Y is the same or different at each occurrence of C (R ¹ ) ₂ , C (R ¹ ) ⁻ , C (═O), NR ¹ , PR ¹ , P (= 0) R ¹ , O or S, particularly preferably C (R ¹ ) ₂ , C (═O) or NR ¹ .

Group Y in another preferred embodiment of the invention, or two groups Y in a particularly preferred embodiment, or all three groups Y in a very particularly preferred embodiment are BR ¹ , C (R ¹ ) ₂ , Si (R ¹ ) ₂ , NR ¹ , PR ¹ , AsR ¹ , P (= O) R ¹ , As (= O) R ¹ , P (= S) R ¹ or As (= S) R ¹ , and C (R ¹ For ₂ ) and Si (R ¹ ) ₂ substituent R ¹ or one of substituents R ¹ represents the group L 2.

Thus a preferred embodiment of the invention is an organic electronic device comprising the compounds of the formulas (4), (5) and (6).

Wherein Z is the same or different during each ^{present, B, B (R 1)} -, C -, CR 1, SiR 1, N, P, As, P (= O), As (= O), P (= S) or As (= S), preferably CR ¹ , N, P or P (= 0) R ¹ , and other symbols and indices have the meanings indicated above.

The compounds of the formulas (5) and (6) are certain embodiments of the compounds of the formula (4). In the compounds of the formula (6), three aromatic groups are bonded in plane to M through the donor atom D, and three groups L2 are bonded in plane to the metal.

Preferred embodiments of the compounds of the formula (6) are the compounds of the formula (6a).

Symbols used herein have the same meaning as described above.

It should be mentioned again here that the substituents R for L2 can form a ring system with the substituents R ¹ for Z.

Although the compounds of formulas (4), (5) and (6) are shown flat, they are also typically represented by the formulas shown above, as schematically shown below for the compounds of formula (6) Similar to the compounds of 1), a three-dimensional structure is employed, where D generally represents a donor atom.

When a plurality of substituents R for different ligand groups L2 form a ring system with each other, as shown below, formation of cryptate is also possible, where V is very generally a ring of a plurality of substituents R A bridge unit formed by closing is shown.

If the bridge group V in the structure shown above represents the group Z, the compounds of the formula (6a) shown above are obtained.

In another preferred embodiment of the compounds of formula (1), the index p = 1, 2 or 3 and the ligand L1 is a ligand of formula (2), ie the metal complex is two, three or It contains four ligands. This preferred embodiment of the compounds of formula (1) is represented by the compounds of formula (7).

Here, the symbols and indices used have the meanings mentioned above and m represents 2, 3 or 4 depending on the metal used. For the main group and the transition metals, m preferably represents 2, and for lanthanides, m may also represent 3 or 4. Furthermore, in these complexes two or more ligands of formula (2) can also be linked by a bridge via two or more groups R or R ¹ which are also linked to one another.

The compounds of formula (7) also adopt a three-dimensional structure, similarly to the compounds of formula (1) shown above, as schematically shown below for m = 2, where D is generally a donor Represents an atom.

In a preferred embodiment of the compounds of the formulas (3) to (7), the symbol D, in each presence, identically or differently, represents C or N. The carbon here is formally negatively charged, ie has a negative charge in the metal free ligand, or is neutral and a carbene carbon atom. If the symbol D represents N or formally represents a negative carbon atom, the positive symbols E bonded to this D preferably represent C at the same time. If symbol D represents a carbene carbon atom, at least one symbol E, particularly preferably both symbols E bonded to this D, preferably represents N, ie Arduengo carbene is preferably present. This preference is due to the special stability of these carbenes.

In more preferred embodiments of the formulas (1) and (3) to (7), the aryl or heteroaryl group formed by EDE together with the group L or Ar is 5 to 20 aromatic ring atoms, particularly preferably Aryl or heteroaryl group having 5 to 14 aromatic ring atoms. It may in each case be substituted by one or more radicals R. Particularly preferred aryl or heteroaryl groups are benzene, phenol, thiophenol, naphthalene, anthracene, phenanthrene, thiophene, pyrrole, furan, pyridine, pyrimidine, pyrazine, pyridazine, triazine, benzothiophene, indole, benzofuran , Quinoline, isoquinoline, quinoxaline, imidazole, pyrazole, benzimidazole, oxazole, thiazole, benzoxazole or benzthiazole, each of which may be substituted by R. Arduengo carbenes are also particularly preferred.

An aryl or heteroaryl group formed by Ar together with the group L in the compounds of the formula (1) or the group EDE in the compounds of the formulas (3) to (7) is represented by the following formulas (8) to (20) Particular preference is given to the compounds of the formulas (1) and (3) to (7), wherein the dotted bonds in each case represent a bond of this group in the ligand, ie a bond to groups Y, each of * Indicates the position of the coordination relative to the metal M.

The symbols used have the same meaning as described above herein, where X represents CR or N, identically or differently in each presence, on the assumption that up to three symbols X in each group represent N . It is preferred that at most two symbols X in each group represent N, it is particularly preferred that at most one symbol X in each group represent N, very particularly preferably all symbols X represent CR.

In another preferred embodiment of the invention, the compound of formula (1) or the compound of formulas (3) to (7) contains at least one direct metal-carbon bond, preferably at least two direct metal-carbon bonds And particularly preferably three direct metal-carbon bonds. These may be bonds from groups L of the ligand of formula (2) or from donor atom D to metal if the donor atom D is identical to carbon in the compounds of formulas (3) to (7). However, they may also be bonds from the group L2 to the metal in the compounds of the formulas (4) to (6).

In a more preferred embodiment of the invention, the groups L 2, in each presence, identically or differently, may be substituted by one or more radicals R and / or may contain 5 to 40 aromatic atoms, which may also contain extraneous donor atoms. Aryl or heteroaryl groups having ring atoms, or neutral or anionic donor groups, which may be bonded to the metal via oxygen, nitrogen, phosphorus or sulfur and may be substituted by one or more radicals R. The aryl or heteroaryl groups here preferably bind to the metal via the ortho-position to the linkage to Z. Preferred aryl and heteroaryl groups are benzene, 2-phenol, 2-thiophenol, naphthalene, anthracene, phenanthrene, pyridine, quinoline, isoquinoline, pyrazine, quinoxaline, pyrimidine, pyridazine, triazine, pyrrole, indole, Imidazole, furan, benzofuran, benzimidazole, pyrazole, triazole, oxazole, thiazole, thiophene, benzothiophene, benzoxazole or benzthiazole, each of which is substituted by one or more radicals R Can be. The binding of the ligand to the group Z and to the metal preferably takes place in these groups via two directly adjacent atoms in these groups, ie via the ortho-position of benzene and the like. Depending on the group, the above-mentioned groups are groups coordinated in a neutral manner which binds via a neutral N atom, for example pyridine, or coordinated in an anionic manner which binds via a negatively charged C or O atom. Groups such as benzene, thiophene and phenol. Other preferred groups L2 are unsaturated or saturated cyclic Arduengo carbenes, in particular unsaturated cyclic Arduengo carbenes, each of which may be substituted by one or more radicals R, and alkenes or imines, each of which is one or more radicals R May be substituted by).

If the group L2 is an aryl or heteroaryl group or an alkene or imine, it is particularly preferably selected from the groups of formulas (21) to (49), wherein in each case the dotted bond is a bond of this group in the ligand, ie a group Represents a bond to Z, in each case * represents a coordination position with respect to the metal M, and the symbols used have the meanings indicated above.

Particularly preferred embodiments of the invention are compounds in which groups (8) to (20) are bonded to groups (21) to (49).

L2 also preferably denotes a neutral or anionic donor group, preferably a monodentate or bidentate chelate group, particularly preferably a monodentate group. The donor atoms here are preferably carbon, oxygen, nitrogen, phosphorus or sulfur, particularly preferably nitrogen or oxygen.

Preferred carbon-containing donor groups are acetylides and aliphatic or aromatic isonitrile.

In addition to the aromatic nitrogen heterocycles mentioned above, preferred nitrogen-containing donor groups contain aliphatic amines, preferably C ₁ -C ₂₀ -alkyl groups, particularly preferably C ₁ -C ₁₀ -alkyl groups, very particularly preferably C ₁ -C ₄ - alkyl groups containing an aliphatic amine, aliphatic cyclic amine, e.g., pyrrolidine, piperidine or morpholine, a nitrile, an amide, an imide and imine, each of which is optionally substituted by groups R Or may be unsubstituted.

Preferred phosphorus-containing donor groups are PF ₂ , P (NR ₂ ) ₂ , wherein R is the same or different in each presence, in the sense given above, a C ₁ -C ₂₀ -alkyl group or aryl or heteroaryl Group, alkyl-, aryl- or mixed alkylarylphosphine, alkylhalo-, arylhalo- or mixed alkylarylhalophosphine, alkyl where in each case the halogen may be F, Cl, Br or I , Aryl or mixed alkyl aryl phosphite or phosphaaromatic compounds, such as phosphabenzene, each of which may be substituted or unsubstituted by groups R. The alkyl groups here are preferably C ₁ -C ₂₀ -alkyl groups, particularly preferably C ₁ -C ₁₀ -alkyl groups, very particularly preferably C ₁ -C ₄ -alkyl groups. Aryl groups are also considered to mean heteroaryl groups. These groups are defined above.

In addition to the phenols mentioned above, preferred oxygen-containing donor groups are alcohols, alcoholates, open chain or cyclic, aliphatic or aromatic ethers, oxygen heterocycles such as furan, aldehydes, ketones, phosphine oxide groups, phosphates, phospho Nates, borates, silicates, sulfoxide groups, carboxylates, phenols, phenolates, oximes, hydroxamates, β-ketoketonates, β-keto esters and β-diesters, each of which is substituted by groups R Or may be unsubstituted, wherein the last mentioned groups represent bidentate chelate ligands. The alkyl group in these groups is preferably a C ₁ -C ₂₀ -alkyl group, particularly preferably a C ₁ -C ₁₀ -alkyl group, very particularly preferably a C ₁ -C ₄ -alkyl group. Aryl groups are also considered to mean heteroaryl groups. These groups are defined above.

In addition to the sulfur hetero-aromatic compounds mentioned above, preferred sulfur-containing donor groups are aliphatic or aromatic thiols and thiolates, open chain or cyclic thioethers, thiocarbonyl groups, phosphine sulfides and thiocarboxylates, respectively May be unsubstituted or substituted by groups R. The alkyl group in these groups is preferably a C ₁ -C ₂₀ -alkyl group, particularly preferably a C ₁ -C ₁₀ -alkyl group, very particularly preferably a C ₁ -C ₄ -alkyl group. Aryl groups are also considered to mean heteroaryl groups. These groups are defined above.

-포스피노카르복실레이트, 글리콜 에테르, 에테르알코올레이트, 디알코올로부터 유도된 디알코올레이트, 예를 들어, 에틸렌 글리콜 또는 1,3-프로필렌 글리콜, 디티올로부터 유도된 디티올레이트, 예를 들어, 1,2-에틸렌디티올 또는 1,3-프로필렌디티올, 디아민, 예를 들어, 에틸렌디아민, 프로필렌디아민 또는 cis- 또는 trans-디아미노시클로헥산, 이민, 예를 들어, 2-[1-(페닐이미노)에틸]피리딘, 2-[1-(2-메틸페닐이미노)에틸]피리딘, 2-[1-(2,6-디-이소-프로필페닐이미노)에틸]피리딘, 2-[1-(메틸이미노)에틸]피리딘, 2-[1-(에틸이미노)에틸]피리딘, 2-[1-(이소-프로필이미노)에틸]피리딘 또는 2-[1-(터트-부틸이미노)에틸]피리딘, 디이민, 예를 들어, 1,2-비스(메틸이미노)에탄, 1,2-비스(에틸이미노)에탄, 1,2-비스(이소-프로필이미노)에탄, 1,2-비스(터트-부틸이미노)에탄, 2,3-비스(메틸이미노)부탄, 2,3-비스(에틸이미노)부탄, 2,3-비스(이소-프로필이미노)부탄, 2,3-비스(터트-부틸이미노)부탄, 1,2-비스(페닐이미노)에탄, 1,2-비스(2-메틸페닐이미노)에탄, 1,2-비스(2,6-디-이소-프로필페닐이미노)에탄, 1,2-비스(2,6-디-터트-부틸페닐이미노)에탄, 2,3-비스(페닐이미노)부탄, 2,3-비스(2-메틸페닐이미노)부탄, 2,3-비스(2,6-디-이소-프로필페닐이미노)부탄 또는 2,3-비스(2,6-디-터트-부틸페닐이미노)부탄, 디포스핀, 예를 들어, 비스(디페닐포스피노메탄), 비스(디페닐포스피노)에탄, 비스(디페닐포스피노)프로판, 비스(디메틸포스피노)메탄, 비스(디메틸포스피노)에탄, 비스(디메틸포스피노)프로판, 비스(디에틸포스피노)메탄, 비스(디에틸포스피노)에탄, 비스(디에틸포스피노)프로판, 비스(디-터트-부틸포스피노)메탄, 비스(디-터트-부틸포스피노)에탄, 비스(터트-부틸포스피노)프로판, 살리실이민으로부터 유도된 살리실이미네이트, 예를 들어, 메틸살리실이민, 에틸살리실이민 또는 페닐살리실이민 등이다. Bidentate chelate groups can also be formed from these donor groups by combining two of these groups, which may be the same or different and may have the same or different donor atoms. These groups may also be substituted by one or more radicals R. Examples of bidentate chelate groups of this kind are carboxylates derived from substituted or unsubstituted β-ketoketonates, β-ketoesters, β-diesters, aminocarboxylic acids, for example pyridine-2-carr Acids, quinoline-2-carboxylic acids, glycine, dimethylglycine, alanine or dimethylaminoalanine, iminoacetoacetonate, hydroxamate, pyridylphosphine,

-Dialcoholates derived from phosphinocarboxylates, glycol ethers, etheralcoholates, dialcohols, for example ethylene glycol or 1,3-propylene glycol, dithiolates derived from dithiols, for example 1,2-ethylenedithiol or 1,3-propylenedithiol, diamines such as ethylenediamine, propylenediamine or cis- or trans-diaminocyclohexane, imines, for example 2- [1- ( Phenylimino) ethyl] pyridine, 2- [1- (2-methylphenylimino) ethyl] pyridine, 2- [1- (2,6-di-iso-propylphenylimino) ethyl] pyridine, 2- [ 1- (methylimino) ethyl] pyridine, 2- [1- (ethylimino) ethyl] pyridine, 2- [1- (iso-propylimino) ethyl] pyridine or 2- [1- (tert-butyl Imino) ethyl] pyridine, diimine, for example 1,2-bis (methylimino) ethane, 1,2-bis (ethylimino) ethane, 1,2-bis (iso-propylimino) Ethane, 1,2-bis (tert-butylimino) ethane, 2,3- S (methylimino) butane, 2,3-bis (ethylimino) butane, 2,3-bis (iso-propylimino) butane, 2,3-bis (tert-butylimino) butane, 1, 2-bis (phenylimino) ethane, 1,2-bis (2-methylphenylimino) ethane, 1,2-bis (2,6-di-iso-propylphenylimino) ethane, 1,2-bis (2,6-di-tert-butylphenylimino) ethane, 2,3-bis (phenylimino) butane, 2,3-bis (2-methylphenylimino) butane, 2,3-bis (2, 6-di-iso-propylphenylimino) butane or 2,3-bis (2,6-di-tert-butylphenylimino) butane, diphosphine, for example bis (diphenylphosphinomethane), Bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (dimethylphosphino) methane, bis (dimethylphosphino) ethane, bis (dimethylphosphino) propane, bis (diethylphosphino) methane To bis (diethylphosphino) ethane, bis (diethylphosphino) propane, bis (di-tert-butylphosphino) methane, bis (di-tert-butylphosphino) Carbonyl, bis (tert-butylphosphino) propane, salicyliminates derived from salicylimines such as methylsalicylimin, ethylsalicylimin or phenylsalicylimin.

Tridentate or polydentate chelate groups may also be formed completely similarly.

Ligands L1 are preferably neutral, monoanionic, dianionic or trianionic ligands, particularly preferably neutral or monoanionic ligands. They are preferably one, two or three digits, ie have one, two or three coordination sites.

Preferred neutral, monodentate ligands L1 are carbon monoxide, isonitrile, for example tert-butyl isonitrile, cyclohexyl isonitrile, adamantyl isonitrile, phenyl isonitrile, mesityl isonitrile, 2,6-dimethylphenyl Isonitrile, 2,6-di-iso-propylphenyl isonitrile, 2,6-di-tert-butylphenyl isonitrile, amines such as trimethylamine, triethylamine, morpholine, phosphine, for example For example, trifluorophosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenylphosphine, tris (pentafluorophenyl) phosphine, phosphite, for example trimethyl phosphine Fight, triethyl phosphite, arsine, for example trifluoroarcin, trimethylarcin, tricyclohexylarcin, tri-tert-butylarcin, triphenylarcinine, tris (pentafluorophenyl Arsine, styrene, for example, tree Fluorostibin, trimethylstibin, tricyclohexylstibin, tri-tert-butylstibin, triphenylstibin, tris (pentafluorophenyl) stibin, and nitrogen-containing heterocyclic compounds, for example , Pyridine, pyridazine, pyrazine, pyrimidine, triazine.

The preferred mono-anionic, one place the ligand L1 is a hydride, a deuterium storage, halides F, Cl, Br and I, an alkyl acetyl fluoride, for example, methyl -C≡C ^-, tert-butyl -C≡C ^-, aryl acetyl fluoride, for example, phenyl -C≡C ^-, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, an aliphatic or aromatic alcoholates, for example methanolate, ethanol rate, rate-propanol , Iso-propanolate, tert-butylate, phenolate, aliphatic or aromatic thioalcoholates such as methanethiolate, ethanethiolate, propanethiolate, iso-propanethiolate, tert-thiobutylate, thio Phenolates, amides such as dimethylamide, diethylamide, di-iso-propylamide, morpholide, carboxylates such as acetate, trifluoroacetate , Propionate, benzoate, and anionic, nitrogen-containing heterocyclic compounds such as pyrrolid, imidazolide, pyrazolide. The alkyl group in these groups is preferably a C ₁ -C ₂₀ -alkyl group, particularly preferably a C ₁ -C ₁₀ -alkyl group, very particularly preferably a C ₁ -C ₄ -alkyl group. Aryl groups are also considered to mean heteroaryl groups. These groups are defined above.

Preferred anionic di-or tri-anionic ligands ^{are, O 2 -, S 2 -} , an alkylene knit, and as a result the coordination is with RN = M form, where R is generally a substituent, or N ^{3 -} shows.

Preferred neutral or monoanionic or dianionic bidentate or polydentate ligands L1 are diamines, for example ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, propylenediamine, N, N, N ', N'-tetramethylpropylenediamine, cis- or trans-diaminocyclohexane, cis- or trans-N, N, N', N'-tetramethyldiaminocyclohexane, imine, for example 2- [1- (phenylimino) ethyl] pyridine, 2- [1- (2-methylphenylimino) ethyl] pyridine, 2- [1- (2,6-di-iso-propylphenylimino) ethyl] pyridine , 2- [1- (methylimino) ethyl] pyridine, 2- [1- (ethylimino) ethyl] pyridine, 2- [1- (iso-propylimino) ethyl] pyridine, 2- [1- (Tert-butylimino) ethyl] pyridine, diimine, for example 1,2-bis (methylimino) ethane, 1,2-bis (ethylimino) ethane, 1,2-bis (iso- Propylimino) ethane, 1,2-bis (tert-butylimino) ethane, 2,3-bis (methylimino) butane, 2,3-bis (ethylimino) butane , 2,3-bis (iso-propylimino) butane, 2,3-bis (tert-butylimino) butane, 1,2-bis (phenylimino) ethane, 1,2-bis (2-methylphenyl Imino) ethane, 1,2-bis (2,6-di-iso-propylphenylimino) ethane, 1,2-bis (2,6-di-tert-butylphenylimino) ethane, 2,3 -Bis (phenylimino) butane, 2,3-bis (2-methylphenylimino) butane, 2,3-bis (2,6-di-iso-propylphenylimino) butane, 2,3-bis ( 2,6-di-tert-butylphenylimino) butane, heterocyclic compounds containing two nitrogen atoms, for example 2,2'-bipyridine, o-phenanthroline, diphosphine, for example For example, bis (diphenyl phosphino) methane, bis (diphenyl phosphino) ethane, bis (diphenyl phosphino) propane, bis (dimethyl phosphino) methane, bis (dimethyl phosphino) ethane, bis (dimethyl phosphino) Propane, bis (diethylphosphino) methane, bis (diethylphosphino) ethane, bis (diethylphosphino) propane, bis (di-tert-butylphosphi) No) methane, bis (di-tert-butylphosphino) ethane, bis (tert-butylphosphino) propane, 1,3-diketonate derived from 1,3-diketone, for example acetylacetone, 3-ketonate derived from benzoylacetone, 1,5-diphenylacetylacetone, dibenzoylmethane, bis (1,1,1-trifluoroacetyl) methane, 3-ketoester, for example ethyl acetoacetate Carboxylates derived from aminocarboxylic acids, for example pyridine-2-carboxylic acid, quinoline-2-carboxylic acid, glycine, N, N-dimethylglycine, alanine, N, N-dimethylaminoalanine Salicylimines derived from salicylimines, for example methylsalicylimines, ethylsalicylimines, phenylsalicylimines, dialcolates derived from dialcohols such as ethylene glycol, 1,3- Propylene glycol, and dithiolates derived from dithiols, for example 1,2-ethylenedithiol, 1,3 -Propylenedithiol.

Preferred tridentate ligands are borates of nitrogen-containing heterocyclic compounds, for example tetrakis (1-imidazolyl) borate and tetrakis (1-pyrazolyl) borate.

More preferred are the bidentate monoanionic ligands L1 which, together with the metal, form a ring metalized five-membered ring containing at least one metal-carbon bond. These are in particular ligands commonly used in the field of phosphorescent metal complexes for organic electroluminescent devices, ie ligands of the kind, such as phenylpyridine, naphthylpyridine, phenylquinoline, phenylisoquinoline, etc., each of which is one or more It may be substituted by radicals R. Many of these ligands are known to those skilled in the art of phosphorescent electroluminescent devices, and those skilled in the art can, without further advancement, select additional ligands of this kind as ligand L1 of the compounds of formula (1). The combination of the two groups shown above by the formulas (21) to (49) is generally particularly suitable for this purpose, where one group is bonded via a neutral nitrogen atom or carbene atom and the other group is negatively charged Through a carbon atom or a negatively charged nitrogen atom. Ligand L1 can then be formed by combining these groups with one another from the groups of the formulas (21) to (49), in the bond represented by the dotted line bond in each case.

Likewise preferred ligands L 1 are η ⁵ -cyclopentadienyl, η ⁵ -pentamethylcyclopentadienyl, η ⁶ -benzene or η ⁷ -cycloheptatrienyl, each of which may be substituted by one or more radicals R Can be.

Likewise preferred ligands L1 are 1,3,5-cis-cyclohexane derivatives, in particular 1,3,5-cis-cyclohexane derivatives of formula (50), 1,1,1-tri (methylene) methane derivatives, in particular 1,1,1-tri (methylene) methane derivatives of formula (51) and 1,1,1-trisubstituted methane, in particular 1,1,1-trisubstituted methane of formula (52).

Here is shown in coordinating the formula, each of the metal M, R has the meaning mentioned above, and A are the same or different as O when each present ^{-, S -, COO -,} P (R) 2 , or N (R) ₂ is represented.

Further preferred embodiments of the present invention are organic electronic devices comprising at least one compound of the formulas (53), (54) and (55).

Where M, X, Y, L1, R, R ¹ , n and p have the meanings mentioned above, and

D represents the same or different C, N or CO ⁻ in each presence.

Particularly preferred embodiments of the invention are compounds of formulas (53) to (55), wherein one group Y, two groups Y or all three groups Y are BR ¹ , C (R ¹ ) ₂ , Si (R ¹ ) ₂ , NR ¹ , PR ¹ , AsR ¹ , P (= O) R ¹ , As (= O) R ¹ , P (= S) R ¹ or As (= S) R ¹ , and C (R ¹⁾ _2, and Si (R ¹⁾ ₂ substituent in one of the R ¹ or the substituent R ¹ represents the group L2. That is, particularly preferred embodiments of the present invention are compounds of the following formulas (56) to (64).

Where the symbols and indices have the meanings indicated above. The groups L2 here are the same or different at each occurrence, whereby groups of the formulas (21) to (49) shown above are preferred.

Particularly preferred embodiments of the compounds of formula (8) are the compounds of formula (65).

Here, symbols and indices have the same meaning as described above.

Preferred embodiments of the compounds of the formulas (53) to (55) and (56) to (65) are those already mentioned in detail above for the compounds of the formulas (3) to (7).

More preferred are the compounds of formulas (3) to (7) and (53) to (65), wherein R is the same or differently in each presence H, deuterium, F, CN, 1-6 Straight chain alkyl or alkoxy groups having C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 6 C atoms, each of which may be substituted by one or more radicals R ² , wherein one or more non-adjacent CH ₂ Groups may be replaced by R ² C═CR ² , O or S, one or more H atoms may be replaced by F), or in each case may be substituted by one or more radicals R ² An aryl or heteroaryl group having 16 to 16 aromatic ring atoms, or a diarylamino group having 10 to 20 aromatic ring atoms which may be substituted by one or more radicals R ² , or a combination of these systems; Two or more substituents R here may also form a monocyclic or polycyclic aliphatic, aromatic and / or benzo-condensed ring system with one another. The symbol R is particularly preferably identical or different in each presence H, deuterium, F, a straight chain alkyl group having 1 to 4 C atoms or a branched alkyl group having 3 or 4 C atoms, each of which is one or more radicals Which may be substituted by R ² , wherein one or more H atoms may be replaced by F), or an aryl group having 6 to 10 aromatic ring atoms that may be substituted by one or more radicals R ² ; Two or more substituents R here may also form a monocyclic or polycyclic aliphatic, aromatic and / or benzo-condensed ring system with one another.

The complexes of formula (1) can in principle be prepared by various processes, but the processes described below prove to be particularly suitable. Complexes of formula (1) are obtained by reaction of a metal alkoxide of formula (66), a metal ketoketonate of formula (67), or a metal halide of formula (68) with a ligand of formula (2) and Optionally obtained by reaction with additional ligands L1.

Here, M and R ² have the same meaning as described above, and the following applies to other symbols and indices.

Hal is the same or different at each occurrence, either F, Cl, Br or I;

Lig, when present, is the same or differently, a neutral or monoanionic, monodentate or bidentate ligand, for example a halide or hydroxide;

q is, at each occurrence, identically or differently, 0, 1, 2, 3 or 4, preferably 0, 1 or 2;

r is, equally or differently, at each occurrence, 1, 2, 3, 4 or 5, wherein r in formulas (66) and (68) represents the valence of the metal M;

The compound of formula (67) may also be charged and may also contain counter ions; The compounds of formulas (66) to (68), in particular of formula (68) may also be in hydrate form.

Complex-like synthesis of ligands likewise reacts the precursors of the ligand with the metal compounds of formula (66), (67) or (68) and then further converts the metal complexes formed in this manner to the finished ligand. It is possible.

Synthesis can be activated, for example, thermally, photochemically or by microwave radiation. The synthesis of tris-ortho-metalized metal complexes is generally described in WO 02/060910, WO 04/085449, WO 04/108738 and WO 07/065523. The synthesis processes and preferred reaction conditions shown in this specification can be applied similarly to the synthesis of the compounds of formula (1). Preferred starting compounds of the iridium complexes are the compounds of the formula (67), in particular the compound Na [IrCl ₂ (acac) ₂ ], and the compounds of the formula (68) in hydrate form, in particular IrCl ₃ hydrate.

These processes allow the complexes to be readily obtained in high purity, preferably with purity> 99%, particularly preferably> 99.9%, according to ¹ H-NMR or HPLC.

Examples of preferred compounds of the formula (1) are the compounds (1) to (307) shown below. These complexes can be prepared, inter alia, by applying the synthetic method described above.

The above-mentioned complexes of the formulas (1) and (3) to (7) shown above, and preferred embodiments, are used as active ingredients in electronic devices. The active ingredient is generally organic or inorganic materials introduced between the anode and the cathode, for example charge-injection, charge-transport or charge-blocking materials, but in particular emitting materials and matrix materials. The compounds according to the invention exhibit particularly good properties for these functions, in particular as emitting materials in organic electroluminescent devices, as described in more detail below. Thus, a preferred embodiment of the present invention is an organic electroluminescent device.

The organic electroluminescent device comprises a cathode, an anode and at least one emitting layer. In addition to these layers, there are also additional layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, charge generating layers in each case. And / or organic or inorganic p / n junctions. For example, an intermediate layer having an exciton blocking function can likewise be introduced between two emitting layers. However, it should be noted that each of these layers does not necessarily exist. The organic electroluminescent device may comprise one emitting layer or may comprise a plurality of emitting layers, wherein at least one emitting layer is of formula (1) or of formulas (3) to (7) At least one compound. If there are a plurality of emitting layers, it preferably has a plurality of emission maximums of 380 nm to 750 nm in total, resulting in white emission as a whole, ie various emitting compounds capable of emitting fluorescence or phosphorescence in the emitting layer. Used. Particular preference is given to three-layer systems, in which the three layers exhibit blue, green and orange or red emission (for the basic structure, see for example WO 05/011013).

In a preferred embodiment of the invention, the organic electronic device comprises a compound of formula (1) or of formulas (3) to (7), or of a preferred embodiment, as indicated above as the emitting compound in the emitting layer. This is especially the case when metal M is a transition metal, in particular iridium.

If the compound of formula (1) or of formulas (3) to (7) is employed as the emitting compound in the emitting layer, it is preferably employed in combination with one or more matrix materials. The mixture of the compound of formula (1) or of the formulas (3) to (7) and the matrix material is based on the mixture as a whole including the emitter and the matrix material, or of the formulas (3) to (3) to 1 to 99% by weight, preferably 2 to 90% by weight, particularly preferably 3 to 40% by weight and especially 5 to 15% by weight of the compound of formula (7). Correspondingly, the mixture is 99 to 1% by weight, preferably 98 to 10% by weight, particularly preferably 97 to 60% by weight, in particular 95 of the matrix material, based on the mixture as a whole comprising the emitter and the matrix material To 85% by weight.

Suitable matrix materials include ketones, phosphine oxides, sulfoxides and sulfones (eg ketones, phosphine oxides, sulfoxides and sulfones according to WO 04/013080, WO 04/093207, WO 06/005627 or the unpublished application DE 102008033943.1). ), Triarylamine, carbazole derivatives (eg CBP (N, N-biscarbazolylbiphenyl) or WO 05/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 08/086851) Carbazole derivatives), indolocarbazole derivatives (for example indolocarbazole derivatives according to WO 07/063754 or WO 08/056746), azacarbazole (for example EP 1617710, EP 1617711, EP 1731584, azacarbazole according to JP 2005/347160), bipolar matrix material (for example bipolar matrix material according to WO 07/137725), silane (for example silane according to WO 05/111172), azaborol or Boric acid esters (for example azaborole or boric acid esters according to WO 06/117052) , Triazine derivatives (for example triazine derivatives according to unpublished application DE 102008036982.9, WO 07/063754 or WO 08/056746), or zinc complexes (for example to zinc complexes according to EP 652273 or to unpublished application DE 102007053771.0). Zinc complexes). Further suitable as matrix material are the compounds of formula (1) of the present application, as described in more detail below.

In a more preferred embodiment of the present invention, the compound of formula (1) or of formulas (3) to (7) shown above, or of a preferred embodiment, is employed as the matrix material of the emitting compound in the emitting layer. This is especially the case when the metal M is a main group metal, in particular aluminum, gallium or indium.

If the compound of formula (1) or of formulas (3) to (7) shown above, or of a preferred embodiment, is employed as the matrix material of the emitting compound in the emitting layer, It is preferable to be employed in combination with). For the purposes of the present invention, phosphorescence is considered to mean phosphorescence from relatively high spin multiplicity of excited states, ie from spin states> 1, in particular from excited triplets or from MLCT mixed states. For the purposes of the present invention, it is intended that all luminescent transition metal complexes from the second and third transition metal series, in particular all luminescent iridium and platinum complexes, are regarded as triplet emitters. The mixture of the compound of the formula (1) or the formula (3) to the formula (7), or the preferred embodiment, and the releasing compound, as indicated above, is then based on the mixture as a whole including the emitter and the matrix material, 99 to 1% by weight, preferably 98 to 10% by weight, particularly preferably 97 to 60% by weight of the compound of the formula (1) or of the formulas (3) to (7) represented above, or of the preferred embodiment, Especially 95 and 85% by weight. Correspondingly, the mixture is based on the mixture as a whole, including the emitter and the matrix material, from 1 to 99% by weight, preferably from 2 to 90% by weight, particularly preferably from 3 to 40% by weight, in particular from 5 to 15 weight percent.

Suitable phosphorescent compounds are, in particular, compounds which emit light upon suitable excitation, in particular those which emit light in the visible region, and also have a number of atoms greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. The branch contains at least one atom. The phosphorescent emitters used are preferably compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular compounds containing iridium or palladium.

Examples of the emitters described above are found by the applications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614, WO 05/033244 or unpublished application DE 102008015526.8. Further suitable as emitters are the above-mentioned compounds of the formula (1) or of the formulas (3) to (7), or preferred embodiments shown above. In general, all phosphorescent complexes used according to the prior art for phosphorescent OLEDs and known to those skilled in the art of organic electroluminescence are suitable, and those skilled in the art can use further phosphorescent complexes without further progress.

In a more preferred embodiment of the invention, the compound of formula (1) or of formulas (3) to (7), or of a preferred embodiment, as indicated above, is employed and / or employed as a hole block material in the hole blocking layer It is employ | adopted as an electron carrying material in an electron carrying layer. In particular, this is the case where the metal M is a main group metal, in particular an alkali metal, alkaline earth metal, aluminum, gallium or indium. The emissive layer can here be fluorescent or phosphorescent.

In a more preferred embodiment of the invention, the compound of formula (1) or of formulas (3) to (7) shown above, or of a preferred embodiment, is employed as a hole transport material in the hole transport layer and / or It is employed as an electron blocking or exciton blocking material in the blocking layer.

More preferred is an organic electroluminescent device, characterized in that one or more layers are formed via a sublimation method, wherein the materials are deposited in a vacuum sublimation unit at an initial pressure of less than 10 ⁻⁵ mbar, preferably less than 10 ⁻⁶ mbar. -deposition). It is also possible for the initial pressure to be lower, for example less than 10 ⁻⁷ mbar.

Likewise preferred is an organic electroluminescent device characterized in that one or more layers are formed via OVPD (Organic Vapor Phase Deposition) method or with the aid of carrier gas sublimation, wherein the materials are at a pressure of 10 ⁻⁵ mbar to 1 bar. Is formed. A special case of this method is the Organic Vapor Jet Printing (OVJP) method, where the materials are formed directly through the nozzle and structured (eg MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301). .

One or more layers may be removed from the solution, for example by spin coating, or in any desired printing process (eg screen printing, flexographic printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing). More preferred is an organic electroluminescent device, which is produced by inkjet printing). Soluble compounds are required for this purpose, and the soluble compounds are obtained, for example, by suitable substitution.

These methods are known to those skilled in the art in ordinary terms and are known to those skilled in the art in organic electroluminescent devices comprising the compounds of formula (1) or of formulas (3) to (7), or preferred embodiments, as indicated above without problems. Can be applied.

Preferred metal complexes of formulas (4) to (7) and (6a) are novel and thus likewise are components of the invention. The preferences indicated above for organic electronic devices also apply completely similarly to the metal complexes according to the invention.

The present invention also relates to the reaction of the corresponding free ligand of the formula (2) or the following formulas (69) to (71) with the metal compounds of the formulas (66), (67) or (68) shown above And a process for preparing the compounds of the formulas (4) to (7) and (6a).

The present invention also relates to compounds of the following formulas (69) to (71). These compounds are free ligands of the metal complexes of formulas (4) to (6) according to the invention, ie valuable intermediates for the synthesis of metal complexes according to the invention.

Wherein the following compounds are excluded from the present invention:

The symbols and indices here have the meanings mentioned above, wherein if groups D and L2 are bonded to the metal M as anionic groups in the complex, the groups D and L2 additionally each carry a hydrogen atom. In addition, the same preferences described above for metal complexes apply completely similarly to free ligands.

The compounds according to the invention described above, in particular compounds substituted by reactive leaving groups such as bromine, iodine, boric acid or boric acid esters, are used as monomers for the production of corresponding oligomers, dendrimers or polymers. Oligomerization or polymerization is preferably carried out here via halogen functionality or boric acid functionality.

The invention therefore also relates to oligomers, polymers or dendrimers comprising one or more compounds of formula (1) or of formulas (3) to (7), wherein the one or more bonds are of From the metal complexes of formulas (3) to (7) as polymers, oligomers or dendrimers. Depending on the linking of the compound of formula (1) or of the formulas (3) to (7), the complex thus forms a side chain of the oligomer or polymer or is linked in the main chain. Polymers, oligomers or dendrimers may be conjugated, partially conjugated or nonconjugated. Oligomers or polymers may be linear, branched or dendritic.

The same preferences as described above apply completely similarly to the repeating units of formula (1) or of formulas (3) to (7) in oligomers, dendrimers or polymers.

For the preparation of oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with other monomers. The units of formula (1) or of formulas (3) to (7) are preferably present in an amount of 0.01 to 50 mol%, particularly preferably in a range of 0.1 to 20 mol%. Suitable and preferred comonomers forming the polymer backbone include fluorene (eg fluorene according to EP 842208 or WO 00/22026), spirobifluorene (eg EP 707020, EP 894107 or WO 06/061181). Spirobifluorene), para-phenylene (eg para-phenylene by WO 92/18552), carbazole (eg carbazole by WO 04/070772 or WO 04/113468) , Thiophenes (eg thiophenes according to EP 1028136), dihydrophenanthrenes (eg dihydrophenanthrenes according to WO 05/014689), cis- and trans-indenofluorenes (eg Cis- and trans-indenofluorenes according to WO 04/041901 or WO 04/113412, ketones (eg ketones according to WO 05/040302), phenanthrene (eg WO 05/104264 or Phenanthrene according to WO 07/017066), or also a plurality of these units. The total proportion of these units is preferably in the range of at least 50 mol%. Polymers, oligomers and dendrimers may also comprise other units, for example hole transport units, in particular hole transport units based on triarylamine, and / or electron transport units.

In addition, the metal complexes according to the invention can also be further functionalized and thus converted into expanded metal complexes. Examples that may be mentioned here are functionalization with arylboric acid by the SUZUKI method or functionalization with primary or secondary amines by the HARTWIG-BUCHWALD method.

Organic electronic devices, in particular organic electroluminescent devices, according to the invention are distinguished by the following surprising advantages over the prior art.

1. Unlike many metal complexes of the prior art, which perform partial or complete thermal decomposition upon sublimation, the compounds according to the invention have a high thermal stability.

2. Organic electroluminescent devices comprising compounds of formula (1) as emitting materials have an excellent lifetime.

3. Blue-phosphorescent complexes having deep blue emission color and long lifetime when used in organic electroluminescent devices are accessible. This is a significant advance over the prior art because until recently blue-phosphorescent devices were only accessible to poor color coordinates and in particular to poor lifetimes.

4. The compounds according to the invention employed in organic electroluminescent devices result in high efficiency and steep current / voltage curves.

These advantages described above are not accompanied by damage to other electronic properties.

The present invention is explained in more detail by the following examples, which are not intended to be limiting. One skilled in the art can formulate other complexes by the present invention from the substrates without progress, and can use them in organic electroluminescent devices or use the process according to the present invention.

Example :

The following synthesis is carried out under protective gas atmosphere in dried solvents, unless otherwise noted. Solvents and reagents can be purchased from ALDRICH or ABCR. The synthesis of ligands 1 to 4 below is carried out according to the literature described.

Ligand 1:

M. Tatazona et al., Macromolecules 1992, 25, 5020.

Ligand 2:

Y. Suzuki et al., Synlett 2005, 2, 263.

Ligand 3:

G. R. Newkome et al., Heterocycles 1978, 9 (11), 1555.

Ligand 4:

In A. N. Vedernikov et al., J. Org. Chem. 2003, 68, 4806.

Additional ligand synthesis:

Example 1 Synthesis of Ligand 5

26.8 g (50 mmol) of 2,6-bis [2- (6-bromo-2-pyridinyl) -1,3-dioxalan-2-yl] pyridine (GR Newkome et al., J. Am. A solution of 300 g of 1,2-propanediol, prepared by Chem. Soc. 1986, 108 (19), 6074) and 2.0 g (50 mmol) of sodium hydrogen sulfide anhydride do. After cooling, the mixture is poured into 500 ml of water and stirred for an additional 12 hours. The solid is filtered off with suction and taken up in a mixture of 50 ml of ethanol and 50 ml of concentrated hydrochloric acid and boiled under reflux for 48 hours. Ethanol is then removed in vacuo, the mixture is made alkaline with solid sodium hydroxide, extracted three times with 50 ml of dichloromethane, and the combined extracts are washed with 100 ml of water, dried over magnesium sulfate and dried Evaporate to state. The oily residue is chromatographed on silica gel (eluent acetone / triethylamine 98: 2) and then recrystallized from acetone. Yield: 2.2 g (7 mmol), 13.9%. Purity 97% by ¹ H-NMR.

Example 2: Synthesis of Ligand 6

To a suspension of 8.3 g (20 mmol) of complex ligand 3-CuCl (Formulation: Example 5) in 200 mL of THF, 20 mL (20 mmol) of potassium triethylborohydride (1 N in THF) The solution of was added with coarse stirring at -78 ° C, and the mixture was stirred for 10 minutes. A solution of 40 mL (80 mmol) of phenyllithium (2 N in di-n-butyl ether) is continuously added dropwise, and the mixture is further stirred at -78 ° C for 1 hour, and then slowly warmed to room temperature. 50 mL of 2 N aqueous sodium cyanide solution is added, the mixture is stirred at room temperature for 12 hours, the aqueous phase is separated off, and the organic phase is evaporated to dryness. The residue is dissolved in 200 ml of chloroform, the insoluble portion is filtered off, and a solution of 32.0 g (240 mmol) of dimethylaminosulfur trifluorolide in 200 ml of chloroform is added dropwise and the mixture is allowed to mix for 30 minutes. During reflux. After cooling, the mixture is hydrolyzed dropwise using 50 ml of cold water and then made alkaline using 250 ml of 4N sodium hydroxide solution. The organic phase is separated off and dried over calcium chloride. After the organic phase is concentrated in vacuo to about 10 ml, 50 ml of methanol is added. After standing for 12 hours, the crystals are filtered off with suction and recrystallized from chloroform / methanol again. Yield: 5.2 g (9 mmol), 46.8%. Purity 97% by ¹ H-NMR.

Synthesis of Metal Complexes:

Example 3: Synthesis of Complex Ligand 1-Cul

A suspension of 3.3 g (10 mmol) of ligand 1, 1.9 g (10 mmol) of copper iodide (I) and 50 g of glass beads (4 mm diameter) in 200 mL of dichloromethane was stirred at room temperature for 24 hours. do. The glass beads were filtered through a coarse sieve, the dichloromethane was concentrated to about 20 mL in vacuo, 50 mL of ethanol was added dropwise, the mixture was stirred for 2 more hours, and the organic crystals were filtered off. Remove, wash twice with 20 mL of ethanol each time and recrystallize from DMSO. Yield: 4.7 g (9.1 mmol), 90.1%. Purity> 99% by ¹ H-NMR.

Example 4: Synthesis of Complex Ligand 2-Cul

Formulated similarly to Example 3, using 5.5 g (10 mmol) of Ligand 2. Yield: 5.5 g (7.5 mmol), 74.6%. Purity> 99% by ¹ H-NMR.

Example 5: Synthesis of Complex Ligand 3-CuCl

Formulated similarly to Example 3, using 3.2 g (10 mmol) of Ligand 3. Yield: 3.9 g (9.3 mmol), 93.3%. Purity> 98% by ¹ H-NMR.

Example 6: Synthesis of Complex Ligand 4-Mo (CO) ₃

A solution of 2.3 g (5 mmol) of ligand 4 and 1.4 g (5 mmol) of cycloheptatriene molybdenum tricarbonyl, in 50 mL of toluene, is heated under reflux for 6 hours, followed by about 10 mL in vacuum Concentrate with and add 50 ml of hexane with stirring. After 12 hours, the crystals are filtered off with suction and washed twice with 10 ml of hexane each time. Yield: 2.6 g (4.1 mmol), 81.8%. Purity> 99% by ¹ H-NMR.

Example 7: Synthesis of Complex Ligand 5-W (CO) ₃

A solution of 1.6 g (5 mmol) of ligand 5, 1.8 g (5 mmol) of tungsten hexacarbonyl and 10 mg of palladium (II) oxide in 50 ml of toluene is heated under reflux for 48 hours. After cooling, the solution is filtered through celite and the filtrate is evaporated. The residue is recrystallized from dichloromethane / hexanes. Yield: 1.6 g (2.7 mmol), 54.0%. Purity> 99% by ¹ H-NMR.

Example 8: Synthesis of Complex Ligand 6-Ir

A mixture of 2.8 g (5 mmol) of ligand 6, 1.5 g (5 mmol) of iridium (III) chloride hydrate and 10 mL of ethylene glycol is stirred at 190 ° C. for 48 hours. After cooling, 100 ml of water are added, the brown precipitate is filtered off, dried and chromatographed on neutral aluminum oxide with dichloromethane / THF (1: 1). Yield: 820 mg (1.1 mmol), 22.0%. Purity> 99% by ¹ H-NMR.

Example 9: Ligand 7-Ir

a) synthesis of ligand precursors:

120 mL of n-butyllithium (2.5 M in hexane) to 53.6 g (100 mmol) of tris (6-bromopyrid-2-yl) fluoromethane in 1500 mL of THF [760177-68-2] To the solution of was added dropwise over a course of 10 minutes with rough stirring at −78 ° C., the mixture was further stirred at −78 ° C. for 30 minutes, and 32.0 mL (315 mmol) of benzaldehyde was then added dropwise. After warming to room temperature, THF is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, washed twice with 200 ml of water, and the organic phase is dried over magnesium sulfate and then evaporated to dryness in vacuo. . Yield: 54.3 g (93 mmol), 93.0%, about 90% by ¹ H-NMR (diastereomer mixture). Viscous oils obtained in this way are employed without further purification.

b) Synthesis of Ligand 7-Ir:

A mixture of 5.8 g (10 mmol) of ligand precursor and 2.4 g (5 mmol) of sodium bisacetylacetonatodichloroiridium in 100 ml of ethylene glycol was stirred at 80 ° C. for 16 hours. Then, the mixture is stirred at 140 ° C. for 24 hours under a continuous air stream of argon. After cooling, 200 ml of water are added to the suspension, the brown solid is filtered off with suction, washed with water and subsequently dried at 70 ° C. in a nitrogen stream. The solid obtained in this way is suspended in 50 ml of glacial acetic acid, 0.5 ml of sulfuric acid is added to the suspension and the mixture is subsequently heated under reflux for 2 hours. After cooling, glacial acetic acid is removed in vacuo, the residue is taken up in 500 ml of dichloromethane, and the organic phase is washed once with 200 ml of saturated hydrocarbon sodium solution, once with 200 ml of water and then dried over magnesium sulfate. Let's do it. After removal of dichloromethane, the residue is chromatographed on silica gel using THF. The yellow solid obtained in this way is then sublimed twice in high vacuum (p = 10 ⁻⁵ mbar, T = 340 ° C.). Yield: 270 mg (0.37 mmol). 7.5%, 99.8% by HPLC.

Example 10 Fabrication and Characterization of Organic Electroluminescent Devices

LEDs are manufactured by the general process outlined below. The general process must, of course, be adjusted in each case according to the particular situation (eg varying the layer thickness to achieve optimum efficiency or color).

General process for the manufacture of OLEDs:

After the ITO-coated substrate (eg, glass support, PET film) is cut to the correct size, it is cleaned in an ultrasonic bath (eg, soap solution, Millipore water, isopropanol) in many cleaning steps. do. During drying, blow into the N ₂ gun and store in the dryer. Prior to vapor coating with organic layers, treatment with an ozone plasma device is performed for about 20 minutes. It may be desirable to use a polymerizable hole injection layer as the first organic layer. This is generally a conjugated, conductive polymer such as polyaniline derivatives (PANI) or polythiophene derivatives (eg PEDOT from BAYER, BAYTRON P ™). This is then applied by spin coating. The organic layers are applied continuously by deposition in a high vacuum unit. The layer thickness and deposition rate of each layer are monitored and controlled through a quartz resonator. It is also possible for the individual layers to consist of more than one compound, ie generally the host material may be doped by the guest material. This is accomplished by co-evaporation from two or more sources. An electrode is also formed in the organic layers. This is usually done by thermal evaporation (Balzer BA360 or Pfeiffer PL S 500). The transparent ITO electrode is continuously contacted as the anode, the metal electrode as the cathode, and the device parameters are determined.

OLEDs having the structure 1 below are manufactured similar to the general process mentioned above.

PEDOT 20 nm (spin-coated from water; spheres from BAYER AG

Persimmon PEDOT; Poly [3,4-ethylenedioxy-2,5-thiophene]

2,2 ', 7,7'-tetrakis (di-p-tolylamino) spiro-9,9'-bifluorene (deposited) at 20 nm

4,4'-bis (1-naphthylphenylamino) biphenyl at NPB 20 nm

(Deposited)

mCP with 10% of the triplet emitter example according to the invention

Doped 20 nm 1,3-bis (N-carbazolyl) benzene (deposition

), See table

2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline at BCP 5 nm

  (Deposited)

AlQ ₃ 30 nm (deposited)

5 nm LiF as Li / Al cathode, 150 nm Al on top

As a non-optimized OLED, this is characterized by standard methods. The table shows the efficiency and voltage and color at 500 cd / m ² .

In addition, OLEDs of Structure 2 below are manufactured similar to the general process mentioned above.

PEDOT 20 nm (spin-coated from water; spheres from BAYER AG

Persimmon PEDOT; Poly [3,4-ethylenedioxy-2,5-thiophene]

PVK 60 nm (spin-coated from chlorobenzene, Aldrich

PVK Mw purchased from 1,100,000 according to Example 4

Solution comprising 5% by weight of one emitter)

10 nm Ba / 150 nm Ag as Ba / Ag cathode

As a non-optimized OLED, this is characterized by standard methods. The table shows the efficiency and voltage and color at 500 cd / m ² .

Claims (16)

An electronic device comprising at least one metal complex of formula (1),

At least one metal complex of formula (1) contains a metal M coordinated to a ligand of formula (2),

The following applies here to the symbols and indices used:
L is, at each occurrence, identically or differently, a substituted or unsubstituted cyclic group, and in each case contains at least one donor atom or C atom or exocyclic donor atom in the ring, The cyclic group is bonded to the metal M; The groups L are connected to each other via groups Y;
Y, at each occurrence, identically or differently, is a substituted or unsubstituted atom from the third, fourth, fifth or sixth main group, in each case connecting two groups L;
L 1, at each occurrence, identically or differently, is a single-, two-, three-, four-, five- or six-membered ligand that binds to the metal M;
n is 0, 1, 2, 3, 4, 5 or 6 in each presence, identically or differently, where n = 0 means that the group Y is absent and a single bond is between two groups L To exist;
p is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; The method of claim 1,
At least one layer comprising an anode, a cathode and at least one compound of formula (1),
Organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic light emitting transistors (O- LETs, organic solar cells (O-SCs), organic photo detectors, organic photoreceptors, organic field-quench devices (O-FQDs), luminescent electrochemical cells (LECs) and organic laser diodes (O -Lasers) and are preferably organic electroluminescent devices. The method according to claim 1 or 2,
And said cyclic group L represents a substituted or unsubstituted aryl or heteroaryl group or a cyclic saturated or unsaturated carbene. The method according to any one of claims 1 to 3,
At least one compound of the formula (3),

Where L1 and p have the same meanings as described above, and the following applies to the symbols and indices used above:
M is a transition metal, lanthanide, alkali metal, alkaline earth metal or main group metal from the third or fourth main group;
D is the presence of, respectively, the same or different, C, N, P, CO ^-, CS ^-, C-NR ₂ or C-PR ₂ (the last mentioned here, four groups are O as hwanoe donor atoms, S , Is bound to the metal via N or P), or CN≡C, wherein this group is bound to the metal via carbon in the extraneous isonitrile group;
E is, at each occurrence, identically or differently, C or N;
Ar, at each occurrence, identically or differently, together with the group EDE, forms an aryl or heteroaryl group having 5 to 40 aromatic ring atoms and is a group which may be substituted by one or more radicals R; Or when D represents a carbene carbon atom, Ar is a group which together with said group EDE form a cyclic saturating group having 5 to 10 ring atoms;
Y is the presence of, respectively, the same or ^{different, BR 1, B (R 1} ) 2 -, C (R 1) -, C (R 1) 2, Si (R 1) -, Si (R 1) ₂ , C (= O), C (= NR), N ⁻ , NR ¹ , N (R ¹ ) ₂ ⁺ , PR ¹ , P (R ¹ ) ₂ ⁺ , AsR ¹ , As (R ¹ ) ₂ ⁺ , P (= O) R ¹ , As (= O) R ¹ , P (= S) R ¹ , As (= S) R ¹ , O, S, S (R ¹ ) ⁺ , Se, Te, S (= O), S (= 0) ₂ , Se (= 0), Se (= 0) ₂ , Te (= 0) or Te (= 0) ₂ ;
R in each presence, identically or differently, H, deuterium, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , Si (R ² ) ₃ , B (OR ² ) ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , having from 1 to 40 C atoms Straight chain alkyl, alkoxy or thioalkoxy groups or straight chain alkenyl or alkynyl groups having 2 to 40 C atoms or branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy groups having 3 to 40 C atoms ( Each may be substituted by one or more radicals R ² , wherein one or more non-adjacent CH ₂ groups are R ² C═CR ² , C≡C, Si (R ² ) ₂ , Ge (R ² ) ₂ , Sn (R ² ) ₂ , C = O, C = S, C = Se, C = NR ² , P (= O) (R ² ), replaced by SO, SO ₂ , NR ² , O, S or CONR ² It may be, and wherein one or more H atoms are values by F, Cl, Br, I, CN or can be substituted by NO _2), or one or more radicals R ² in each case 5 to 60 aromatic aromatic or heteroaromatic ring having ring atoms total, which may be, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ^2, or A diarylamino group, diheteroarylamino group or arylheteroarylamino group having 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R ² , or a combination of these systems; Two or more of these substituents R may also form a monocyclic or polycyclic, aliphatic, aromatic and / or benzo-condensed ring system with one another;
R ^1, at each occurrence, identically or differently, is R or a group L2;
R ² in each presence, identically or differently, is an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having H, F or 1 to 20 C atoms, wherein also one or more H atoms are to be replaced by F Can be; Two or more substituents R ² here may also form a monocyclic or polycyclic, aliphatic or aromatic ring system with one another;
L 2 in each presence, identically or differently, is a donor group having from 1 to 40 C atoms, which can form additional bonds or coordination to the metal M and to one or more radicals R May be substituted by;
n is 0, 1, 2, 3, 4, 5 or 6, provided that each index, identically or differently, at each occurrence cannot represent 0 at the same time, where n = 0 is An electronic device, meaning that there is no group Y and a single bond exists between the two groups L. The method according to any one of claims 1 to 4,
M denotes zirconium, hafnium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, copper, silver, gold, scandium, yttrium, lanthanum, aluminum, gallium or indium . 6. The method according to any one of claims 1 to 5,
Containing the compound of formula (4), formula (5), formula (6), formula (6a) or formula (7),

The formula (4) Z a to (6) in the presence of, respectively, the same or different, B, B (R ^{1) -,} C ^-, CR ^1, SiR ^1, N, P, As, P ( = O), As (= O), P (= S) or As (= S), m represents 2, 3 or 4, other symbols and indices mean as described in claim 1 or 4. An electronic device having a. The method according to any one of claims 1 to 6,
The aryl or heteroaryl group formed by Ar together with the group L in the compounds of the formula (1) or the group EDE of the compounds of the formulas (3) to (7) is represented by the formulas (8) to (20) Represents a group,
Wherein in each case the dotted line bond represents the bond of this group in the ligand, ie to the groups Y, in each case * represents the position of the coordination relative to the metal M,

The symbols used herein have the meanings set forth in claims 1 or 4, and X is the same or different at each occurrence, provided that at most three symbols X in each group represent N, An electronic device representing CR or N. The method according to any one of claims 1 to 7,
Group L2 represents an aryl or heteroaryl group and is selected from the groups of formulas (21) to (49),
Where in each case the dashed bonds represent the binding of this group in the ligand, ie to the group Z, in each case * represents the position of the coordination relative to the metal M, and the symbols used are claims 1 or 3 Have the meaning set forth in this section,

or,
L2 is a carbon-containing donor groups of aliphatic or aromatic acetylides or aliphatic or aromatic isonitriles, nitrogen-containing donor groups of aliphatic amines, aliphatic cyclic amines, nitriles, amides, imides and imines, each substituted by groups R Or unsubstituted), phosphorus-containing donor groups PF ₂ , P (NR ₂ ) ₂ , where R is the same or different at each occurrence, identically or differently, a C ₁ -C ₂₀ -alkyl group or an aryl or heteroaryl group , Alkyl-, aryl- or mixed alkylarylphosphine, alkylhalo-, arylhalo- or mixed alkylarylhalophosphine, alkyl, in which the halogen may in each case be F, Cl, Br or I, Aryl or mixed alkyl aryl phosphite or phosphaaromatic compounds, each of which may be substituted or unsubstituted by groups R), alcohol, alcoholate, open chain or cyclic, aliphatic or aromatic ethers , Oxygen heterocycle, aldehyde, ketone, phosphine oxide group, phosphate, phosphonate, borate, silicate, sulfoxide group, carboxylate, phenol, phenolate, oxime, hydroxamate, β-ketoketonate, β Oxygen-containing donor groups of keto esters and β-diesters, each of which may be substituted or unsubstituted by groups R, aliphatic or aromatic thiols and thiolates, open or cyclic thioethers, thiocarbonyl groups, phosph Sulfur-containing donor groups of fin sulfide and thiocarboxylate, each of which may be substituted or unsubstituted by groups R, or a bidentate chelate group formed from these groups, characterized by a neutral or anionic donor group An electronic device. The method according to any one of claims 1 to 8,
The ligand L1 is carbon monoxide, isonitrile, amine, imine, diimine, phosphine, phosphite, arsine, stibin, nitrogen-containing heterocyclic compound, hydride, deuterated hydride, halide F, Cl, Br And I, alkylacetylides, arylacetylides, cyanides, cyanates, isocyanates, thiocyanates, isothiocyanates, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcolates, amides, carboxylates, anionics, nitrogen-containing heterocyclic compounds, O ^{2 -,} S ^{2 -,} nitrene, N ^{3 -,} a diamine, the two heterocyclic compounds containing nitrogen atoms, diphosphine, derived from 1,3-diketones 1,3 -Diketonates, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, di alcohols derived from dialcohols Alcohol methacrylate, nitrogen-containing heterocyclic compound of a borate, of at least one metal with a metal-bidentate mono-anionic ligand realization form an accelerating five-membered ring containing a carbon bond, η ^{5-cyclopentadienyl,} η ⁵ -Pentamethyl-cyclopentadienyl, η ⁶ -benzene, η ⁷ -cycloheptatrienyl (each of which may also be substituted by R), 1,3,5-cis-cyclohexane derivative, 1,1 , 1-tri (methylene) methane derivative and 1,1,1-trisubstituted methane. The method according to any one of claims 1 to 9,
At least one compound of the formulas (53) to (65),

Wherein M, X, Y, Z, L1, R, R ¹ , n and p have the meanings set forth in claim 1, 3 or 6 and further
D represents C, N or CO ⁻ , identically or differently, in each presence. The method according to any one of claims 1 to 10,
The electronic device,
A cathode, an anode and at least one emitting layer, and in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, charge generating layer And / or an organic electroluminescent device, optionally comprising additional layers selected from organic or inorganic p / n junctions. An organic electroluminescent device according to claim 11,
Compounds of formula (1) or of formulas (3) to (7) are employed as emitting compounds in the emitting layer, preferably in combination with one or more matrix materials,
The compound of formula (1) or formulas (3) to (7) is employed as a matrix material for the emitting compound in the emitting layer,
The compound of formula (1) or formula (3) to formula (7) is employed as the hole blocking material in the hole blocking layer and / or the electron transporting material in the electron transporting layer, or
The compound of formula (1) or (3) to (7) is employed as a hole transporting material in the hole transporting layer and / or an exciton blocking material in the exciton blocking layer. As the compound of Formulas (4) to (7) and (6a),

Wherein the symbols and indices used have the meanings set forth in claim 1, 4 or 6. As a preparation method of the compound of Claim 13,
The compound is prepared and optionally added by reaction of a metal alkoxide of formula (66), a metal ketoketonate of formula (67), or a metal halide of formula (68) with a ligand of formula (2) Prepared by reaction with ligands L1,

Wherein M and R ² have the same meaning as described in claim 1 or 4, and the following applies to other symbols and indices:
Hal is the same or different at each occurrence, either F, Cl, Br or I;
Lig, when present, is the same or differently, a neutral or monoanionic, single or bidentate ligand;
q is, at each occurrence, identically or differently, 0, 1, 2, 3 or 4, preferably 0, 1 or 2;
r is 1, 2, 3, 4 or 5, in each occurrence, identically or differently, wherein r in formulas (66) and (68) represents the valence of said metal M;
The compound of formula (67) may also be charged and may also contain counter ions; Processes for the preparation of compounds wherein the compounds of the formulas (66) to (68), in particular the formula (68), may also be in hydrate form. As a compound of Formula (69)-(71),

Wherein the symbols and indices have the meaning set forth in claim 1, 4 or 6; If groups D and L2 are bonded to the metal M as anionic groups in the complex, the groups D and L2 here additionally each carry a hydrogen atom; The following compound

Is excluded from the present invention. As oligomers, polymers or dendrimers comprising one or more compounds of formula (1) or of formulas (3) to (7),
Oligomers, polymers or dendrimers, wherein one or more bonds are present from the complex of formula (1) or from a complex of formulas (3) to (7) to an oligomer, polymer or dendrimer.